【作者】 贾丽霞；

【导师】 宋心远；

【作者基本信息】 东华大学 ， 纺织化学与染整工程， 2011， 博士

【摘要】 面对国际贸易的“绿色壁垒”,“低碳经济”和“清洁生产”势在必行。新疆已经成为我国重要的纺织基地,必须“开发环保染整技术,生产绿色染整产品”。因此,根据学科研究前沿和前期研究成果,本文从新疆植物中筛选出防紫外性能优良的1,4-萘醌,初步建立天然色素结构类型与羊毛染色性能或防紫外性能的关系。探索环保高效制备萘醌类天然色素等同体或羟基衍生物的新方法,为今后实现产业化生产提供可能。进行萘醌等同体或衍生物的结构修饰,赋予合成色素(染料)更优异的染色性能和防紫外性能。在第二章,主要以新疆的软紫草和指甲花为原料,选择高效低毒的溶剂进行提取。对紫草素进行温和的磺化处理以提高溶解性能及改善染色性能。通过旋转回归试验,确定指甲花醌和磺化紫草素的最佳染色工艺。研究指甲花醌或磺化紫草素的染色性能,选择环境友好型的媒染剂进行媒染。在第三章,主要采用安全与廉价的反应物合成6只萘醌类天然色素等同体及衍生物。设计相关萘醌的有效合成路线,使合成的萘醌含有羟基或多羟基。选择不同的原料和合成方法,引入-CH3、-OCH3或-C1等基团,为进行结构修饰做准备。在第四章,主要重点研究通过碳碳双键构建萘醌类共轭体系,设计和合成二种萘醌非偶氮染料,探索丰富染料色谱和改善染色性能的有效途径。通过设计合成萘醌的羟基数量和位置,为提高媒染性能奠定基础。在第五章,主要研究提取萘醌、磺化紫草素、合成的萘醌等同体,以及经过结构修饰的萘醌衍生物的防紫外性能,并通过荧光光谱进行初步解释。研究结果表明,分别采用4种不同的改进方法进行指甲花醌和紫草素的提取,存在工艺繁琐、纯度难控制及提取率较低等问题,总体认为利用萘醌天然衍生物染色羊毛是不经济和不现实的。指甲花醌、磺化紫草素、合成萘醌等同体及衍生物对羊毛纤维均具有一定的染色性能,但深染性、颜色特性以及染色牢度等受到提取方法、色素类型、染色工艺参数等方面的影响。A13+、Mg2+、Fe3+和Fe2+等环境友好媒染剂能不同程度地提高萘醌色素、合成萘醌衍生物对羊毛织物的媒染性能。研究研究结果还表明,萘醌结构天然色素及其磺化产物具有一定的防紫外性能。认为合成的5-羟基-8-甲基-1,4-萘醌具有优良的防紫外性能,而溶剂法合成的四酮类产物具有优异的防紫外性能。通过测定染料的荧光光谱,认这些色素能受紫外线激发而在395-500 nm间产生荧光,值得深入研究。本文的创新点主要表现在：(1)研究思路的创新：结合新疆丰富的指甲花和软紫草资源优势以及新疆特色毛纺织品染整需求,依据学科前沿和现有研究基础,研究萘醌类天然色素对羊毛的染色性能和防紫外性能；以天然色素等同体为切入点,合成出具有萘醌类天然色素结构特征的色素；融入现代分子设计理念,修饰合成萘醌色素等同体或衍生物结构；结合纺织品生态标准与防紫外性能需求,探索合成防紫外环保染料的新途径。(2)合成方法的创新：通过6-氯-5-羟基-1,4-萘醌的全合成,提出了一种合成萘醌羟基衍生物的新方法。这种方法以安全价廉的丙三醇为原料,采用无溶剂或混合溶剂,使用环境友好型催化剂,具有原料便宜易得、合成过程简单、分离提纯方便、产物收率高等特点。在过程中还合成出另一个重要化合物：3-羟基-4-氯-2-吡喃酮；申请了二项发明专利(201010617028.1以及201010617005.0),目前均处于实质审查阶段；提出了一种用硼酸系制备3.8-二羟基-1,4-萘醌的新方法：以及改进了以2-羟基-1,4-萘醌合成苯并占吨四酮色素的方法。(3)应用技术的创新：将前期已有的“助剂增溶染色”法应用于紫草素的染色。结果证实,在一定范围内,自制增溶剂WP能显著提高紫草素的溶解性能以及羊毛的表观染色深度和色泽鲜艳度。通过温和磺化方法提高紫草素和合成萘醌色素的溶解度,以实现直接上染和媒染,没有查阅到这种萘醌磺化方法和染色应用报道。更多还原

【Abstract】 Faced with the "green barriers" in international trade, "low-carbon economy" and "clean production" are becoming more and more imperative. For Xinjiang, one of the most important textile industry bases in China, it is urged to develop environment-friendly technology and products in native dyeing and finishing industry. According to the research tendency and our previous study, 1,4-naphthoquinone, which has excellent UV protection performance, was chosen as our research direction. In the paper, the relationship between the structure of natural colour (dyes) and wool dyeing properties or UV protection performance was established; new environmentally efficient methods to prepare nature-identical naphthoquinone or naphthoquinone derivatives were developed; with the structural modifications of synthetic naphthoquinone or naphthoquinone derivatives, excellent dyeing properties and UV protection performance were achieved.In chapter two, raw materials, extracting agents, and the dyeing properties of colours extracted were studied. Arnebia euchroma and lawsonia inermis in Xinjing were chosen as raw materials and natural colours were extracted by solvent with high efficiency and low toxicity. Dyeing performance and solubility of colours could be improved by mild sulfonation method. By means of general rotation experiments, the optimistic dyeing processes of lawsone and sulfonated shikonin were established. Dyeing performances of dyes and the mordant dyeing properties with environment-friendly mordants were studied.In chapter three, we studied the synthesis of naphthoquinone colours. Six naphthoquinone colours and derivatives were rynthesized using safe and inexnensive reactants Effective svnthetic route was designed to make the naphthoquinone have one or more hydroxyls (-OH group). With different raw materials and synthetic methods, the groups such as -CH3,-OCH3 or -Cl were introduced to naphthoquinone, which was the preparation of structural modification.In chapter four, the synthesis of non-azo naphthoquinone colours and their mordant dyeing performances were studied. Based on the study of building conjugated systems through carbon-carbon double bonds, two types of naphthoquinone colours were designed and synthesized. The effective methods to enrich colour chromatography and to improve dyeing properties were developed. Through the design and synthesis of the amount and location of hydroxyl on naphthoquinone, the mordant dyeing performances were improved.In chapter five, the UV protection performances of colours were studied. UV protection properties of lawsone and shikonin extracted, sulfonated shikonin, synthetic naphthoquinone and naphthoquinone derivatives treated through structural modification were studied. The preliminary interpretation of UV protection properties was carried out using fluorescence spectroscopy The results showed that four kinds of methods to extract lawsone and shikonin these had some disadvantages such as cumbersome process, hardly controlled purity and low product yield. So it was uneconomic and unrealistic to dye wool fabrics with natural naphthoquinone derivatives. It was found that extracted lawsone and sulfonated shikonin, synthetic naphthoquinone and naphthoquinone derivatives could be used in dying wool fabrics, and the deep-dyeing, chromatic properties and color fastness were affected by some factors such as extracting methods, pigment types and parameters of dyeing process. environment-friendly mordant such as Al3+, Mg2+, Fe3+ and Fe2+ could differently enhance the mordant dyeing performances of naphthoquinone extracted or synthesized on wool fabrics.It was also found that natural naphthoquinone colours and their sulfonation had some UV protection properties. The synthesized 5-hydroxy-8-methyl-1,4-naphthoquinone and 5,8-dihydroxy-1,4-naphthoquinone had excellent UV protection performance and synthesized tetrone colours had more. By measuring fluorescence spectroscopy, it was found that these cholurs could be excited by UV and generated fluorescence between 395 to 500 nm, which was worth further studying.Innovations:(1) Innovation in research idea:In the paper, the native natural sources such as arnebia euchroma and lawsonia inermis and wool fibers, which are widely existed in Xinjiang, were chosen as study objects. The dyeing properties and UV protection performance of natural naphthoquinone were studied. The colours (dyes) which had the same structure with natural naphthoquinone were synthesized. Based on the morden concept of molecular design, synthetic naphthoquinone or naphthoquinone derivatives were modified. According to ecological standards of textiles and the need of UV protection, the new method of UV protection was developed by synthesizing dyes which had the properties of UV protection.(2) Innovation in the method of synthesis: On the basis of total synthesis of 6-chloro-5-hydroxy-1,4-naphthoquinone, a new method to synthesize hydroxy naphthoquinone derivatives was established. In the method, safe and inexpensive glycerol was used as starting materials. At the same time, mixed solvent and environment-friendly catalysts were used. The method had the some advantages such as cheaper raw materials, simple synthetic process, convenient separation and purification process and high product yield. An important compound 3-hydroxy-4-chloro-2-pyrone was also synthesized. Two patents were applied for and patent application numbers were 201010617028.1 and 201010617005.0, which were all in substantive examination phase. In addition, a method to synthesize 5.8-dihvdroxy-1,4-naphthoquinone using (?) acid was established and the (?) of the (?) of tetronc colours with 2-hydroxy-1,4-naphthoquinone was improved.(3) Innovation in applied technology: The method that increasing solubility of shikonin by-additives was applied to the dyeing. It was found that self-made solubilizing agent WP could improve the solubility of shikonin and the apparent dyeing depth and the brightness on wool fabrics. Mild sulfonation approach was used to enhance the solubility of shikonin extracted and naphthoquinone colours synthesized, which enable their good using in direct dyeing and mordant dyeing.更多还原